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EP1179579B1 - Fluorkohlenwasserstoffzusammensetzungen - Google Patents

Fluorkohlenwasserstoffzusammensetzungen Download PDF

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Publication number
EP1179579B1
EP1179579B1 EP01202969A EP01202969A EP1179579B1 EP 1179579 B1 EP1179579 B1 EP 1179579B1 EP 01202969 A EP01202969 A EP 01202969A EP 01202969 A EP01202969 A EP 01202969A EP 1179579 B1 EP1179579 B1 EP 1179579B1
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EP
European Patent Office
Prior art keywords
hfc
composition
compositions
azeotrope
weight percent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01202969A
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English (en)
French (fr)
Other versions
EP1179579A3 (de
EP1179579A2 (de
Inventor
Barbara Haviland Minor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/943,420 external-priority patent/US6261472B1/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1179579A2 publication Critical patent/EP1179579A2/de
Publication of EP1179579A3 publication Critical patent/EP1179579A3/de
Application granted granted Critical
Publication of EP1179579B1 publication Critical patent/EP1179579B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/30—Materials not provided for elsewhere for aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/11—Ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/32—The mixture being azeotropic

Definitions

  • the present invention relates to the discovery of compositions which include 2-fluoropropane with at least one of tetrafluoroethane, difluoroethane, propane or dimethylether.
  • compositions are useful as aerosol propellants, refrigerants, cleaning agents, expansion agents for polyolefins and polyurethanes, refrigerants, heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.
  • Fluorinated hydrocarbons have had many uses, such as aerosol propellants, blowing agents and refrigerants. These compounds include trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12) and chlorodifluoromethane (HCFC-22).
  • HFCs Hydrofluorocarbons
  • refrigerant In refrigeration applications, a refrigerant is often lost during operation through leaks in shaft seals, hose connections, soldered joints and broken lines. In addition, the refrigerant may be released to the atmosphere during maintenance procedures on refrigeration equipment. If the refrigerant is not a pure component or an azeotropic or azeotrope-like composition, the refrigerant composition may change when leaked or discharged to the atmosphere from the refrigeration equipment. The change in refrigerant composition may cause the refrigerant to become flammable or to have poor refrigeration performance.
  • a single fluorinated hydrocarbon or an azeotropic or azeotrope-like composition that includes one or more fluorinated hydrocarbons.
  • Fluorinated hydrocarbons which are classified as low or non-VOC are also useful as aerosol propellants or blowing agents because they do not contribute significantly to ground level pollution.
  • WO 94/02563 describes the use of mixtures of 1,1,2,2-tetrafluoroethane (HFC-134) and 2-fluoropropane (HFC-281ea) for use in refrigeration, as blowing agents and as aerosol propellants.
  • Fluorinated hydrocarbons may also be used as cleaning agents or solvent to clean, for example, electronic circuit boards. It is desirable that the cleaning agents be azeotropic or azeotrope-like because in vapor degreasing operations the cleaning agent is generally redistilled and reused for final rinse cleaning.
  • Azeotropic or azeotrope-like compositions that include a fluorinated hydrocarbon are also useful as blowing agents in the manufacture of closed-cell polyurethane, phenolic and thermoplastic foams, as heat transfer media, gaseous dielectrics, fire extinguishing agents or power cycle working fluids such as for heat pumps. These compositions may also be used as inert media for polymerization reactions, fluids for removing particulates from metal surfaces, as carrier fluids that may be used, for example, to place a fine film of lubricant on metal parts or as buffing abrasive agents to remove buffing abrasive compounds from polished surfaces such as metal.
  • They are also used as displacement drying agents for removing water, such as from jewelry or metal parts, as resist developers in conventional circuit manufacturing techniques including chlorine-type developing agents, or as strippers for photoresists when used with, for example, a chlorohydrocarbon such as 1,1,1-trichloroethane or trichloroethylene.
  • compositions which include 2-fluoropropane. These compositions have zero ozone depletion potential (ODP), low global warming potential and are lower VOC than hydrocarbons. These compositions are also useful as pure components or with at least one of tetrafluoroethane, difluoroethane, hexafluoropropane, a hydrocarbon or dimethylether.
  • ODP ozone depletion potential
  • compositions are used as aerosol propellants, refrigerants, cleaning agents, expansion agents for polyolefins and polyurethanes, heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.
  • the invention relates to the discovery of binary azeotropic or azeotrope-like compositions comprising effective amounts of 2-fluoropropane and a second component of tetrafluoroethane, difluoroethane, propane or dimethylether, to form an azeotropic or azeotrope-like composition.
  • Azeotropes are highly desirable for refrigerants but not necessary for aerosol propellants.
  • the compounds of the present invention include the following components:
  • HFC-281ea (isopropyl fluoride, CAS Reg. No. 420-26-8) has been prepared by reaction of hydrogen fluoride with ethylene and propylene, respectively, as reported by Grosse and Lin in J. Org. Chem., Vol. 3, pp. 26-32 (1938 ) .
  • the present invention relates to the following compositions:
  • 1-99 wt.% of each of the components of the compositions are useful as aerosol propellants, refrigerants, cleaning agents, expansion agents for polyolefins and polyurethanes, refrigerants, heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.
  • the present invention also relates to the discovery of azeotropic or azeotrope-like compositions of effective amounts of each of the above mixtures to form an azeotropic or azeotrope-like composition.
  • azeotropic composition is meant a constant boiling liquid admixture of two or more substances that behaves as a single substance.
  • One way to characterize an azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without compositional change.
  • Constant boiling compositions are characterized as azeotropic because they exhibit either a maximum or minimum boiling point, as compared with that of the non-azeotropic mixtures of the same components.
  • azeotrope-like composition is meant a constant boiling, or substantially constant boiling, liquid admixture of two or more substances that behaves as a single substance.
  • azeotrope-like composition One way to characterize an azeotrope-like composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without substantial composition change.
  • Another way to characterize an azeotrope-like composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially the same.
  • a composition is azeotrope-like if, after 50 weight percent of the composition is removed such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is less than about 10 percent, when measured in absolute units.
  • absolute units it is meant measurements of pressure and, for example, psia, atmospheres, bars, torr, dynes per square centimeter, millimeters of mercury, inches of water and other equivalent terms well known in the art. If an azeotrope is present, there is no difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed.
  • compositions that are azeotropic there is usually some range of compositions around the azeotrope point that, for a maximum boiling azeotrope, have boiling points at a particular pressure higher than the pure components of the composition at that pressure and have vapor pressures at a particular temperature lower than the pure components of the composition at that temperature, and that, for a minimum boiling azeotrope, have boiling points at a particular pressure lower than the pure components of the composition at that pressure and have vapor pressures at a particular temperature higher than the pure components of the composition at that temperature.
  • Boiling temperatures and vapor pressures above or below that of the pure components are caused by unexpected intermolecular forces between and among the molecules of the compositions, which can be a combination of repulsive and attractive forces such as van der Waals forces and hydrogen bonding.
  • compositions that have a maximum or minimum boiling point at a particular pressure, or a maximum or minimum vapor pressure at a particular temperature may or may not be coextensive with the range of compositions that have a change in vapor pressure of less than about 10% when 50 weight percent of the composition is evaporated.
  • Substantially constant boiling, azeotropic or azeotrope-like compositions of this invention comprise the following: COMPONENTS T°C WEIGHT RANGES PREFERRED (wt.%/wt.%) (wt.%/wt.%) HFC-281ea/HFC-134a -10 1-99/1-99 10-90/10/90 HFC-281ea/HFC-152a -20 1-99/1-99 10-90/10-90 NEC-281ea/propane -10 1-41/59-99 1-41/59-99 HFC-281ea/DME -9.95 1-99/1-99 10-90/10-90
  • effective amount is defined as the amount of each component of the inventive compositions which, when combined, results in the formation of an azeotropic or azeotrope-like composition.
  • This definition includes the amounts of each component, which amounts may vary depending on the pressure applied to the composition so long as the azeotropic or azeotrope-like compositions continue to exist at the different pressures, but with possible different boiling points.
  • effective amount includes the amounts, such as may be expressed in weight percentages, of each component of the compositions of the instant invention which form azeotropic or azeotrope-like compositions at temperatures or pressures other than as described herein.
  • azeotropic or constant-boiling is intended to mean also essentially azeotropic or essentially-constant boiling.
  • included within the meaning of these terms are not only the true azeotropes described above, but also other compositions containing the same components in different proportions, which are true azeotropes at other temperatures and pressures, as well as those equivalent compositions which are part of the same azeotropic system and are azeotrope-like in their properties.
  • compositions which contain the same components as the azeotrope, which will not only exhibit essentially equivalent properties for refrigeration and other applications, but which will also exhibit essentially equivalent properties to the true azeotropic composition in terms of constant boiling characteristics or tendency not to segregate or fractionate on boiling.
  • azeotrope or azeotrope-like compositions of the present invention can be prepared by any convenient method including mixing or combining the desired amounts.
  • a preferred method is to weight the desired component amounts and thereafter combine them in an appropriate container.
  • a vessel is charged with an initial composition at a specified temperature, and the initial vapour pressure of the composition is measured.
  • the composition is allowed to leak from the vessel, while the temperature is held constant, until 50 weight percent of the initial composition is removed, at which time the vapor pressure of the composition remaining in the vessel is measured.
  • Vapor pressures of the compounds of the present invention are given below. The data indicate these compounds are useful replacements for hydrocarbons widely used in aerosol formulations today. HFC-281ea and isobutane have nearly identical vapor pressures. Kauri-butanol values for the compounds of the present invention are also higher than each respective hydrocarbon. This indicates these compounds have better solvent capability as well as compatibility with aerosol resins and other active ingredients.
  • the compounds of the present invention have significantly reduced photochemical (hydroxyl radical) reactivity compared to hydrocarbons propane, butane and isobutane widely used in aerosols today.
  • Using the compounds of the present invention in aerosols can significantly reduce ground level smog.
  • HFC-3-10-1sy could be classified as non-VOC because its reactivity is less than ethane.
  • HFC-281ea is significantly less reactive than its hydrocarbon analogue isobutane.
  • a 55% VOC (volatile organic compound) hair spray in accordance with the present invention is formulated as follows: TABLE Wt% Octylacrylamide/acrlyates/butylaminoethyl methacrylate copolymer (National Starch) 5.00 5.00 AMP (2-amino-2-methyl- 1 -propanol, Kodak) 0.96 Dimethicone silylate (Hydrolabs) 0.50 Water 3.54
  • the vapor pressure of each mixture may vary with formulation. This example is illustrative and does not reflect an optimized system.
  • Two 55% VOC hair sprays in accordance with the present invention are formulated as follows: A B Component Wt% Wt% PVM/MA Copolymer 6.00 6.00 AMP 0.35 0.35 Water 29.05 38.65 Ethanol 40-1 34.60 25.00
  • the vapor pressure of each mixture may vary with formulation. This example is illustrative and does not reflect an optimized system.
  • the formulations containing HFC-28 lea will have less impact on ground level smog than those containing hydrocarbons because HFC-28 lea has less significantly less photochemical reactivity.
  • a fragrance in accordance with the present invention is formulated as follows: TABLE Wt% Fragrance 3.0 Ethanol 40-1 70.0 Water 15.0
  • the vapor pressure of each mixture may vary with formulation. This example is illustrative and does not reflect an optimized system.
  • the formulations containing HFC-281ea will have less impact on ground level smog than those containing hydrocarbons because HFC-281ea has less significantly less photochemical reactivity.
  • the following example demonstrates efficacy of the patent invention in hair sprays, compared to a widely used hydrofluorocarbon propellant HFC-152a (CH 3 CHF 2 ) as shown in the table below.
  • HFC-152a hydrofluorocarbon propellant
  • the formulations were one phase indicating complete miscibility. Tack and dry times, curl droop, and flame extension tests were used to evaluate performance. Curl droop measures the percent lengthening of a curl five minutes after spraying. Flame extension was measured to determine the flammability of each formulation. Results show each formulation achieved 80% or higher curl retention, good tack and dry times, and acceptable flame extensions despite the fact that the formulations were not optimized.
  • the refrigeration capacity is based on a compressor with a fixed displacement of 3.5 cubic feet (99 liters) per minute and 75% volumetric efficiency.
  • Capacity is intended to mean the change in enthalpy of the refrigerant in the evaporator per pound (0.454 kg) of refrigerant circulated, i.e. the heat removed by the refrigerant in the evaporator per time.
  • Coefficient of performance (COP) is intended to mean the ratio of the capacity to compressor work. It is a measure of refrigerant energy efficiency. Evap Cond Capacity Refrig Press Press Comp. Dis BTU/min Comp.
  • Additives such as lubricants, corrosion inhibitors, surfactants, stabilizers, dyes and other appropriate materials may be added to the novel compositions of the invention for a variety of purposes provides they do not have an adverse influence on the composition for its intended application.
  • Preferred lubricants include esters having a molecular weight greater than 250.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Detergent Compositions (AREA)

Claims (5)

  1. Azeotrope oder azeotropähnliche Zusammensetzung umfassend 1 - 99 Gewichtsprozent 2-Fluorpropan und 99 - 1 Gewichtsprozent mindestens eines von 1,1,1,2-Tetrafluorethan, 1,1-Difluorethan, Propan oder Dimethylether.
  2. Azeotrope oder azeotropähnliche Zusammensetzung nach Anspruch 1, wobei die Zusammensetzung im Wesentlichen aus: 1 - 99 Gewichtsprozent 2-Fluorpropan und 99 - 1 Gewichtsprozent 1,1,1,2-Tetrafluorethan; 1 - 99 Gewichtsprozent 2-Fluorpropan und 99 - 1 Gewichtsprozent 1,1-Difluorethan; 1 - 41 Gewichtsprozent 2-Fluorpropan und 99 - 59 Gewichtsprozent Propan; oder 1 - 99 Gewichtsprozent 2-Fluorpropan und 99 -1 Gewichtsprozent Dimethylether besteht.
  3. Verfahren zum Erzeugen eines Aerosols umfassend die Verwendung einer Zusammensetzung nach Anspruch 1 oder Anspruch 2.
  4. Verfahren zum Erzeugen von Kühlung umfassend das Kondensieren einer Zusammensetzung nach Anspruch 1 oder Anspruch 2 und daraufhin das Verdampfen der Zusammensetzung in der Nähe des zu kühlenden Körpers.
  5. Verfahren zum Erzeugen eines Duroplast- oder Thermoplastschaumstoffs, umfassend die Verwendung einer Zusammensetzung nach Anspruch 1 oder Anspruch 2 als Blähmittel.
EP01202969A 1996-11-04 1997-11-03 Fluorkohlenwasserstoffzusammensetzungen Expired - Lifetime EP1179579B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US299796P 1996-11-04 1996-11-04
US2997P 1996-11-04
US943420 1997-10-03
US08/943,420 US6261472B1 (en) 1996-11-04 1997-10-03 Azeotrope-like compositions containing fluoroethane
EP97946444A EP0938527B1 (de) 1996-11-04 1997-11-03 Zusammensetzungen aus fluorkohlenwasserstoffen

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP97946444A Division EP0938527B1 (de) 1996-11-04 1997-11-03 Zusammensetzungen aus fluorkohlenwasserstoffen

Publications (3)

Publication Number Publication Date
EP1179579A2 EP1179579A2 (de) 2002-02-13
EP1179579A3 EP1179579A3 (de) 2004-01-07
EP1179579B1 true EP1179579B1 (de) 2009-03-11

Family

ID=40459242

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01202969A Expired - Lifetime EP1179579B1 (de) 1996-11-04 1997-11-03 Fluorkohlenwasserstoffzusammensetzungen

Country Status (4)

Country Link
EP (1) EP1179579B1 (de)
DE (1) DE69739305D1 (de)
DK (1) DK1179579T3 (de)
ES (1) ES2321804T3 (de)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2665400B2 (ja) * 1992-07-15 1997-10-22 イー・アイ・デュポン・ドゥ・ヌムール・アンド・カンパニー １，１，２，２−テトラフルオロエタンを含む冷媒組成物
EP0669966A1 (de) * 1992-11-19 1995-09-06 E.I. Du Pont De Nemours And Company Kühlzusammensetzung die 1,1,2-trifluorethan enthält
WO1996015205A1 (en) * 1994-11-16 1996-05-23 E.I. Du Pont De Nemours And Company Compositions that include a cyclic fluorocarbon
US5558810A (en) * 1994-11-16 1996-09-24 E. I. Du Pont De Nemours And Company Pentafluoropropane compositions

Also Published As

Publication number Publication date
DK1179579T3 (da) 2009-06-22
ES2321804T3 (es) 2009-06-12
EP1179579A3 (de) 2004-01-07
EP1179579A2 (de) 2002-02-13
DE69739305D1 (de) 2009-04-23

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